KR102323942B1 - Etching solution composition for indium oxide layer and method for etching copper-based metal layer using the same - Google Patents
Etching solution composition for indium oxide layer and method for etching copper-based metal layer using the same Download PDFInfo
- Publication number
- KR102323942B1 KR102323942B1 KR1020150010538A KR20150010538A KR102323942B1 KR 102323942 B1 KR102323942 B1 KR 102323942B1 KR 1020150010538 A KR1020150010538 A KR 1020150010538A KR 20150010538 A KR20150010538 A KR 20150010538A KR 102323942 B1 KR102323942 B1 KR 102323942B1
- Authority
- KR
- South Korea
- Prior art keywords
- indium oxide
- oxide film
- etchant composition
- indium
- etching
- Prior art date
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- 229910003437 indium oxide Inorganic materials 0.000 title claims abstract description 130
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 239000000203 mixture Substances 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000005530 etching Methods 0.000 title claims description 51
- 239000010949 copper Substances 0.000 title claims description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 27
- 229910052802 copper Inorganic materials 0.000 title claims description 20
- 229910052751 metal Inorganic materials 0.000 title claims description 13
- 239000002184 metal Substances 0.000 title claims description 13
- 239000000758 substrate Substances 0.000 claims abstract description 42
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 25
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- -1 azole compound Chemical class 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 13
- 239000011737 fluorine Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 9
- 239000010408 film Substances 0.000 claims description 151
- 239000000463 material Substances 0.000 claims description 11
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 9
- 239000010409 thin film Substances 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 229910000431 copper oxide Inorganic materials 0.000 claims description 7
- 239000004065 semiconductor Substances 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 5
- 239000011698 potassium fluoride Substances 0.000 claims description 5
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 5
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims description 5
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 3
- 229920002120 photoresistant polymer Polymers 0.000 claims description 3
- 235000003270 potassium fluoride Nutrition 0.000 claims description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003236 pyrrolines Chemical class 0.000 claims description 2
- 239000003352 sequestering agent Substances 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 claims description 2
- 150000003536 tetrazoles Chemical class 0.000 claims description 2
- 150000003852 triazoles Chemical class 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 11
- 230000000052 comparative effect Effects 0.000 description 32
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DEPDDPLQZYCHOH-UHFFFAOYSA-N 1h-imidazol-2-amine Chemical compound NC1=NC=CN1 DEPDDPLQZYCHOH-UHFFFAOYSA-N 0.000 description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- 229910017855 NH 4 F Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- MKBBSFGKFMQPPC-UHFFFAOYSA-N 2-propyl-1h-imidazole Chemical compound CCCC1=NC=CN1 MKBBSFGKFMQPPC-UHFFFAOYSA-N 0.000 description 1
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- NJQHZENQKNIRSY-UHFFFAOYSA-N 5-ethyl-1h-imidazole Chemical compound CCC1=CNC=N1 NJQHZENQKNIRSY-UHFFFAOYSA-N 0.000 description 1
- HPSJFXKHFLNPQM-UHFFFAOYSA-N 5-propyl-1h-imidazole Chemical compound CCCC1=CNC=N1 HPSJFXKHFLNPQM-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- ILRLTAZWFOQHRT-UHFFFAOYSA-N potassium;sulfuric acid Chemical compound [K].OS(O)(=O)=O ILRLTAZWFOQHRT-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/30—Acidic compositions for etching other metallic material
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/1303—Apparatus specially adapted to the manufacture of LCDs
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
- G02F1/1362—Active matrix addressed cells
- G02F1/136286—Wiring, e.g. gate line, drain line
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
- G02F1/1362—Active matrix addressed cells
- G02F1/136286—Wiring, e.g. gate line, drain line
- G02F1/136295—Materials; Compositions; Manufacture processes
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Nonlinear Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Mathematical Physics (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Thin Film Transistor (AREA)
- Liquid Crystal (AREA)
- Weting (AREA)
Abstract
본 발명은 인듐산화막 식각액 조성물 및 이를 이용한 액정 표시 장치용 어레이 기판의 제조방법에 관한 것으로, 보다 자세하게는 황산염 또는 초산염을 포함하지 않고, 질산, 아졸 화합물, 함불소 화합물 및 물을 포함하는 인듐산화막 식각액 조성물 및 이를 이용한 액정 표시 장치용 어레이 기판의 제조방법에 관한 것이다.The present invention relates to an indium oxide film etchant composition and a method for manufacturing an array substrate for a liquid crystal display using the same, and more particularly, to an indium oxide film etchant containing nitric acid, an azole compound, a fluorine-containing compound, and water without including sulfate or acetate. It relates to a composition and a method of manufacturing an array substrate for a liquid crystal display using the same.
Description
본 발명은 인듐산화막 식각액 조성물 및 이를 이용한 액정 표시 장치용 어레이 기판의 제조방법에 관한 것으로, 보다 자세하게는 황산염 또는 초산염을 포함하지 않고, 질산, 아졸 화합물, 함불소 화합물 및 물을 포함하는 인듐산화막 식각액 조성물 및 이를 이용한 액정 표시 장치용 어레이 기판의 제조방법에 관한 것이다.The present invention relates to an indium oxide film etchant composition and a method for manufacturing an array substrate for a liquid crystal display using the same, and more particularly, to an indium oxide film etchant containing nitric acid, an azole compound, a fluorine-containing compound, and water without including sulfate or acetate. It relates to a composition and a method of manufacturing an array substrate for a liquid crystal display using the same.
액정 표시 소자(liquid crystal display device, LCD device)는 뛰어난 해상도에 따른 선명한 영상을 제공하며 전기를 적게 소모하고, 디스플레이 화면을 얇게 만들 수 있게 하는 특성 때문에 평판 디스플레이 장치 중 가장 각광을 받고 있다. 오늘날 이러한 액정 표시 소자를 구동하는 전자 회로로서 대표적인 것은 박막 트랜지스터(thin film transistor, TFT) 회로로서 전형적인 박막 트랜지스터 액정표시(TFT-LCD) 소자는 디스플레이 화면의 화소(pixel)를 이루고 있다. TFT-LCD 소자에서 스위칭 소자로 작용하는 TFT는 매트릭스 형태로 배열한 TFT용 기판과 그 기판을 마주 보는 컬러 필터 기판 사이에 액정 물질을 채워 제조한 것이다. TFT-LCD의 전체 제조 공정은 크게 TFT 기판 제조 공정, 컬러 필터 공정, 셀 공정, 모듈 공정으로 나뉘는데, 정확하고 선명한 영상을 나타내는데 있어서 TFT 기판과 컬러 필터 제조 공정의 중요성은 매우 크다.A liquid crystal display device (LCD device) is receiving the most spotlight among flat panel display devices because it provides a clear image according to an excellent resolution, consumes less electricity, and allows a display screen to be made thin. A typical electronic circuit driving such a liquid crystal display device today is a thin film transistor (TFT) circuit. A typical thin film transistor liquid crystal display (TFT-LCD) device constitutes a pixel of a display screen. A TFT that acts as a switching element in a TFT-LCD device is manufactured by filling a liquid crystal material between a TFT substrate arranged in a matrix and a color filter substrate facing the substrate. The entire TFT-LCD manufacturing process is largely divided into a TFT substrate manufacturing process, a color filter process, a cell process, and a module process. The importance of the TFT substrate and color filter manufacturing process is very high in displaying accurate and clear images.
TFT-LCD 장치의 화소 표시 전극 제조에는 투명한 광학적 특성을 가지면서 전기 전도도가 높은 물질로 된 박막이 필요한데, 현재 산화인듐(indium oxide)을 기반으로 한 산화인듐주석(Indium Tin Oxide, ITO)과 산화인듐아연(Indium Zinc Oxide, IZO)이 투명도전막의 재료로 쓰이고 있다. In order to manufacture a pixel display electrode for a TFT-LCD device, a thin film made of a material with high electrical conductivity while having transparent optical properties is required. Currently, indium tin oxide (ITO) and oxide based on indium oxide are required. Indium Zinc Oxide (IZO) is used as a material for the transparent conductive film.
또한, 화소표시 전극에 원하는 전기회로의 선로를 구현하려면 회로 패턴대로 박막층을 깎아내는 식각(蝕刻, etching) 과정이 필요하다.In addition, in order to implement a desired electric circuit line on the pixel display electrode, an etching process is required to cut the thin film layer according to the circuit pattern.
그러나 금속 이중층의 식각에 흔히 쓰이는 기존 식각액으로는 산화물인 ITO의 강한 내화학성 때문에 ITO나 IZO소재의 투명도전막을 에칭하기 어려웠다. 구체적으로 왕수(aqua regia, HCl+CH3COOH+HNO3)나 염산제2철(Ⅲ)의 염산 용액(FeCl3/HCl), 옥살산수용액이 투명도전막 습식 식각액이 사용되어 왔지만, 왕수계 식각액 또는 염산제2철의 염산 용액을 이용하여 ITO 막을 식각하는 경우 가격은 저렴하나 패턴의 측면에서 더 빨리 식각되서 프로파일(profile)이 불량하며, 식각액을 조성한 후 염산 또는 질산이 휘발하기 때문에 식각액 조성물의 변동이 심하고, 하부 금속에 화학적 어택(Attack)을 발생시킬 수 있다. 대한민국 공개특허 제10-2000-0017470호에는 옥살산(Oxalic Acid)을 이용하여 비정질 ITO(amorphous Indium Tin Oxide)를 식각하였지만, 이러한 경우 ITO 패턴 주위에 잔사가 발생하기 쉬우며, 저온에서 옥살산의 용해도가 낮아 석출물이 발생하여 식각 장비 고장을 발생시키는 문제가 있다.However, it was difficult to etch a transparent conductive film made of ITO or IZO material because of the strong chemical resistance of ITO, an oxide, with the conventional etchant commonly used for etching metal double layers. Specifically, aqua regia (HCl+CH 3 COOH+HNO 3 ), hydrochloric acid solution of ferric (III) hydrochloride (FeCl 3 /HCl), and oxalic acid aqueous solution have been used as a transparent conductive film wet etching solution, but aqua regia-based etching solution or When the ITO film is etched using a hydrochloric acid solution of ferric hydrochloride, the price is low, but the profile is poor because it is etched faster in terms of the pattern. This is severe and may cause chemical attack on the underlying metal. In Korean Patent Publication No. 10-2000-0017470, amorphous indium tin oxide (ITO) is etched using oxalic acid, but in this case, residues are likely to occur around the ITO pattern, and the solubility of oxalic acid at low temperature There is a problem that precipitates are generated due to the low level, which causes the failure of the etching equipment.
또한, HI로 이루어진 식각액의 경우, 식각 속도가 크고 측면 식각이 적지만, 가격이 비싸고, 독성과 부식성이 크며, 투명 화소전극 하부에 위치한 데이터 배선에 어택을 발생시킴에 따라 실제 공정에 사용하기에는 한계가 있는 문제점이 있다.In addition, in the case of an etchant made of HI, the etching rate is high and the side etching is small, but it is expensive, highly toxic and corrosive, and it is difficult to use in the actual process as it causes an attack on the data wiring located under the transparent pixel electrode. There is a problem with
또한, 대한민국 공개특허 제10-2010-0053175호에는 함할로겐 화합물, 보조산화제, 식각조절제, 잔사억제제, 부식억제제 및 물을 포함하는 투명도전막 식각 조성물에 관한 내용이 공개되어 있으며, 식각조절제 및 잔사억제제로 각각 황산염 및 초산염이 사용되었다. 그러나, 상기 황산염 및 초산염을 식각 조성물에 포함할 경우, 횡방향의 식각 속도가 느려 사이드 식각량이 적으며, 하부막을 손상시키는 문제점이 발생한다.In addition, Korean Patent Laid-Open No. 10-2010-0053175 discloses a transparent conductive film etching composition comprising a halogen-containing compound, an auxiliary oxidizing agent, an etch control agent, a residue inhibitor, a corrosion inhibitor, and water, and an etch control agent and a residue inhibitor Sulfate and acetate were used respectively. However, when the sulfate and acetate are included in the etching composition, the etching rate in the lateral direction is slow, the amount of side etching is small, and a problem of damaging the lower layer occurs.
본 발명은 인듐산화막 식각액 조성물로 황산염 및 초산염으로 이루어진 군으로부터 선택되는 1종 이상을 포함하지 않음으로써, 빠른 속도로 인듐산화막을 효과적으로 식각할 수 있어 식각 공정의 효율성을 극대화 시키는 것을 목적으로 한다.An object of the present invention is to maximize the efficiency of the etching process by not including at least one selected from the group consisting of sulfate and acetate as the indium oxide film etchant composition, so that the indium oxide film can be effectively etched at a fast rate.
또한, 본 발명은 인듐산화막의 하부막에 대한 손상을 최소화하여 박막트랜지스터-액정표시소자(TFT-LCD)의 구동 특성을 향상시키는 것을 목적으로 한다.Another object of the present invention is to improve driving characteristics of a thin film transistor-liquid crystal display device (TFT-LCD) by minimizing damage to the lower layer of the indium oxide layer.
따라서, 본 발명은 상기 식각 공정의 효율성 및 박막트랜지스터-액정표시소자(TFT-LCD)의 구동 특성을 향상시킬 수 있는 인듐산화막 식각액 조성물, 이를 이용한 식각 방법 및 액정 표시 장치용 어레이 기판의 제조 방법을 제공하는 것을 목적으로 한다.Accordingly, the present invention provides an indium oxide film etchant composition capable of improving the efficiency of the etching process and driving characteristics of a thin film transistor-liquid crystal display device (TFT-LCD), an etching method using the same, and a method of manufacturing an array substrate for a liquid crystal display device intended to provide
상기 목적을 달성하기 위하여,In order to achieve the above object,
본 발명은 황산염 및 초산염으로 이루어진 군으로부터 선택되는 1종 이상을 포함하지 않으며, The present invention does not include at least one selected from the group consisting of sulfates and acetates,
인듐산화막 식각액 조성물 총 중량에 대하여, 질산 3 내지 30 중량%, 아졸 화합물 0.1 내지 10 중량%, 함불소 화합물 0.01 내지 5 중량% 및 인듐산화막 식각액 조성물 총 중량이 100 중량%가 되도록 잔량의 물을 포함하는 것을 특징으로 하는 인듐산화막 식각액 조성물을 제공한다.Based on the total weight of the indium oxide film etchant composition, 3 to 30% by weight of nitric acid, 0.1 to 10% by weight of the azole compound, 0.01 to 5% by weight of the fluorine-containing compound, and the remaining amount of water so that the total weight of the indium oxide film etchant composition is 100% by weight It provides an indium oxide film etchant composition, characterized in that.
또한, 본 발명은 (1)기판 상에 인듐산화막을 형성하는 단계;In addition, the present invention comprises the steps of (1) forming an indium oxide film on a substrate;
(2)상기 인듐산화막 상에 선택적으로 광반응 물질을 남기는 단계; 및(2) selectively leaving a photoreactive material on the indium oxide layer; and
(3)상기 본 발명의 인듐산화막 식각액 조성물을 사용하여 상기 인듐산화막을 식각하는 단계를 포함하는 인듐산화막의 식각방법을 제공한다.(3) It provides an etching method of an indium oxide film comprising the step of etching the indium oxide film using the indium oxide film etchant composition of the present invention.
또한, 본 발명은 (1)기판 상에 게이트 배선을 형성하는 단계;In addition, the present invention comprises the steps of (1) forming a gate wiring on a substrate;
(2)상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계;(2) forming a gate insulating layer on the substrate including the gate wiring;
(3)상기 게이트 절연층 상에 산화물 반도체층을 형성하는 단계;(3) forming an oxide semiconductor layer on the gate insulating layer;
(4)상기 산화물 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및(4) forming source and drain electrodes on the oxide semiconductor layer; and
(5)상기 드레인 전극에 연결된 화소 전극을 형성하는 단계를 포함하는 액정표시장치용 어레이 기판의 제조방법에 있어서,(5) In the method of manufacturing an array substrate for a liquid crystal display device comprising the step of forming a pixel electrode connected to the drain electrode,
상기 (1)단계는 기판 상에 구리/인듐산화막 또는 구리합금/인듐산화막을 형성하고, 상기 구리/인듐산화막 또는 구리합금/인듐산화막을 식각액 조성물로 식각하여 게이트 배선을 형성하는 단계를 포함하고,The step (1) comprises forming a copper/indium oxide film or a copper alloy/indium oxide film on a substrate, and etching the copper/indium oxide film or copper alloy/indium oxide film with an etchant composition to form a gate wiring,
상기 (5)단계는 인듐산화막을 형성하고, 상기 인듐산화막을 식각액 조성물로 식각하여 화소 전극을 형성하는 단계를 포함하며, The step (5) includes forming an indium oxide layer and etching the indium oxide layer with an etchant composition to form a pixel electrode,
상기 식각액 조성물은 상기 본 발명의 인듐산화막 식각액 조성물인 것을 특징으로 하는 액정 표시 장치용 어레이 기판의 제조방법을 제공한다.The etchant composition provides a method of manufacturing an array substrate for a liquid crystal display, characterized in that the indium oxide film etchant composition of the present invention.
또한, 본 발명은 상기 본 발명의 인듐산화막 식각액 조성물을 사용하여 식각된 게이트 배선 및 화소 전극으로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 액정 표시 장치용 어레이 기판을 제공한다.In addition, the present invention provides an array substrate for a liquid crystal display comprising at least one selected from the group consisting of a gate wire and a pixel electrode etched using the indium oxide film etchant composition of the present invention.
본 발명의 인듐산화막 식각액 조성물은 황산염 및 초산염으로 이루어진 군으로부터 선택되는 1종 이상을 포함하지 않음으로써, 식각 속도를 개선하여 인듐산화막을 효과적으로 식각할 수 있어 식각 공정의 효율성을 향상시킬 수 있다.The indium oxide layer etchant composition of the present invention does not contain at least one selected from the group consisting of sulfate and acetate, thereby improving the etching rate to effectively etch the indium oxide layer, thereby improving the efficiency of the etching process.
또한, 본 발명의 인듐산화막 식각액 조성물은 인듐산화막의 하부막인 구리계 금속막의 손상을 최소화할 수 있어 박막트랜지스터-액정표시소자(TFT-LCD)의 구동 특성을 향상시킬 수 있으며, 기판의 크기가 커도 식각 균일성이 유지되는 장점을 지니고 있다.In addition, the indium oxide film etchant composition of the present invention can minimize damage to the copper-based metal film, which is the lower film of the indium oxide film, thereby improving the driving characteristics of the thin film transistor-liquid crystal display device (TFT-LCD), and the size of the substrate Even if it is large, it has the advantage of maintaining etch uniformity.
이하, 본 발명을 보다 자세히 설명한다.
Hereinafter, the present invention will be described in more detail.
본 발명은 황산염 및 초산염으로 이루어진 군으로부터 선택되는 1종 이상을 포함하지 않으며, The present invention does not include at least one selected from the group consisting of sulfates and acetates,
인듐산화막 식각액 조성물 총 중량에 대하여, 질산 3 내지 30 중량%, 아졸 화합물 0.1 내지 10 중량%, 함불소 화합물 0.01 내지 5 중량% 및 인듐산화막 식각액 조성물 총 중량이 100 중량%가 되도록 잔량의 물을 포함하는 것을 특징으로 하는 인듐산화막 식각액 조성물에 관한 것이다.
Based on the total weight of the indium oxide film etchant composition, 3 to 30% by weight of nitric acid, 0.1 to 10% by weight of the azole compound, 0.01 to 5% by weight of the fluorine-containing compound, and the remaining amount of water so that the total weight of the indium oxide film etchant composition is 100% by weight It relates to an indium oxide film etchant composition, characterized in that
본 발명의 인듐산화막 식각액 조성물은 황산염 및 초산염으로 이루어진 군으로부터 선택되는 1종 이상을 포함하지 않음으로써, 인듐산화막을 보다 빠른 속도로 식각할 수 있어 식각 공정의 효율성을 증대시킬 수 있다.
Since the indium oxide film etchant composition of the present invention does not contain at least one selected from the group consisting of sulfate and acetate, the indium oxide film can be etched at a faster rate, thereby increasing the efficiency of the etching process.
본 발명에서 인듐산화막은 인듐주석산화막(ITO), 인듐아연산화막(IZO) 및 인듐갈륨아연산화막(IGZO)으로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것이다.In the present invention, the indium oxide film includes at least one selected from the group consisting of an indium tin oxide film (ITO), an indium zinc oxide film (IZO), and an indium gallium zinc oxide film (IGZO).
또한, 본 발명의 인듐산화막 식각액 조성물로 식각되는 인듐산화막은, 인듐산화막으로 이루어진 단일막; 또는 상기 단일막과 구리계 금속막으로 구성되는 다층막이며, 상기 구리계 금속막은 구리막 또는 구리합금막일 수 있다. 상기 합금막은 질화막 또는 산화막도 포함하는 개념이다.
In addition, the indium oxide film etched with the indium oxide film etchant composition of the present invention may include a single film made of an indium oxide film; Alternatively, it may be a multilayer film including the single film and the copper-based metal film, and the copper-based metal film may be a copper film or a copper alloy film. The alloy film is a concept including a nitride film or an oxide film.
본 발명의 인듐산화막 식각액 조성물에 포함되는 질산(HNO3)은 인듐산화막의 주산화제로, 인듐산화막을 식각하는 역할을 한다. 또한, 인듐산화막에 대하여 빠른 식각속도를 가져 식각 공정에서 요구되는 큰 사이드 에칭을 확보할 수 있게 한다. Nitric acid (HNO 3 ) contained in the indium oxide film etchant composition of the present invention is a main oxidizing agent for the indium oxide film, and serves to etch the indium oxide film. In addition, it is possible to secure a large side etching required in the etching process by having a fast etching rate with respect to the indium oxide layer.
상기 질산은 인듐산화막 식각액 조성물 총 중량에 대하여, 3 내지 30 중량%로 포함되며, 바람직하게는 5 내지 25 중량%로 포함된다. 상기 질산이 3 중량% 미만으로 포함되면 인듐산화막의 식각 속도가 저하될 수 있으며, 30 중량%를 초과하면 인듐산화막 하부 및 인접한 금속에 화학적 손상을 발생시킬 수 있을 뿐만 아니라, 식각속도가 지나치게 빨라져 공정 컨트롤이 어려운 문제가 발생한다.
The nitric acid is included in an amount of 3 to 30% by weight, preferably 5 to 25% by weight, based on the total weight of the indium oxide film etchant composition. If the nitric acid content is less than 3 wt%, the etching rate of the indium oxide film may be reduced, and if it exceeds 30 wt%, chemical damage may be caused to the lower portion of the indium oxide film and the adjacent metal, and the etching rate may be excessively fast, so that the process There are problems that are difficult to control.
본 발명의 인듐산화막 식각액 조성물에 포함되는 아졸 화합물은 액정 표시 장치용 어레이 기판의 화소 전극으로 사용되는 인듐산화막과 접촉하게 되는 구리 배선에 손상을 최소화하는 역할을 한다. 즉, 인듐산화막의 하부막인 구리계 금속막의 손상을 최소화하는 역할을 한다.The azole compound included in the indium oxide film etchant composition of the present invention serves to minimize damage to the copper wiring that comes into contact with the indium oxide film used as a pixel electrode of an array substrate for a liquid crystal display. That is, it serves to minimize damage to the copper-based metal layer, which is the lower layer of the indium oxide layer.
상기 아졸 화합물은 바람직하게는 트리아졸계(triazole), 테트라졸계(tetrazole), 이미다졸계(imidazole), 인돌계(indole), 푸린계(purine), 피라졸계(pyrazole), 피리딘계(pyridine), 피리미딘계(pyrimidine), 피롤계(pyrrole), 피롤리딘계(pyrrolidine) 및 피롤린계(pyrroline) 화합물로 이루어진 군으로부터 선택되는 1종 이상을 포함한다.The azole compound is preferably a triazole, tetrazole, imidazole, indole, purine, pyrazole, pyridine, and at least one selected from the group consisting of pyrimidine, pyrrole, pyrrolidine and pyrroline compounds.
또한, 보다 구체적으로, 아미노테트라졸, 벤조트리아졸, 톨릴트리아졸, 2-메틸이미다졸, 2-에틸이미다졸, 2-프로필이미다졸, 2-아미노이미다졸, 4-메틸이미다졸, 4-에틸이미다졸 및 4-프로필이미다졸로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것이 바람직하다.In addition, more specifically, aminotetrazole, benzotriazole, tolyltriazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-aminoimidazole, 4-methylimidazole It is preferable to include at least one selected from the group consisting of sol, 4-ethylimidazole and 4-propylimidazole.
상기 아졸 화합물은 인듐산화막 식각액 조성물 총 중량에 대하여, 0.1 내지 10 중량%로 포함되며, 바람직하게는 0.5 내지 5 중량%로 포함된다. 상기 아졸 화합물이 0.1 중량% 미만으로 포함되면, 인듐산화막의 하부막인 구리막에 손상이 가해질 수 있으며, 10 중량%를 초과하면 구리막의 손상은 방지할 수 있으나, 인듐산화막의 식각 속도가 저하될 수 있다.
The azole compound is included in an amount of 0.1 to 10 wt%, preferably 0.5 to 5 wt%, based on the total weight of the indium oxide layer etchant composition. When the azole compound is included in an amount of less than 0.1% by weight, damage may be applied to the copper film, which is the lower layer of the indium oxide film, and when it exceeds 10% by weight, damage to the copper film can be prevented, but the etching rate of the indium oxide film may be lowered. can
본 발명의 인듐산화막 식각액 조성물에 포함되는 함불소 화합물은 인듐산화막 식각시 잔사를 제거하는 역할을 한다. The fluorine-containing compound included in the indium oxide film etchant composition of the present invention serves to remove residues during etching of the indium oxide film.
상기 함불소 화합물은 용액 내에서 플루오르 이온 또는 다원자 플로오르 이온으로 해리될 수 있는 것이라면 특별히 한정하지는 않으나, 불화암모늄(ammonium fluoride: NH4F), 불화나트륨(sodium fluoride: NaF), 불화칼륨(potassium fluoride: KF), 중불화암모늄(ammonium bifluoride: NH4F·HF), 중불화나트륨(sodium bifluoride: NaF·HF) 및 중불화칼륨(potassium bifluoride: KF·HF)으로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것이 바람직하다.The fluorine-containing compound is not particularly limited as long as it can be dissociated into fluorine ions or polyatomic fluorine ions in solution, but ammonium fluoride (NH 4 F), sodium fluoride (NaF), potassium fluoride ( 1 selected from the group consisting of potassium fluoride: KF), ammonium bifluoride (NH 4 F HF), sodium bifluoride (NaF HF) and potassium bifluoride (KF HF) It is preferred to include more than one species.
또한, 상기 함불소 화합물은 인듐산화막 식각액 조성물 총 중량에 대하여, 0.01 내지 5 중량%로 포함되며, 바람직하게는 0.01 내지 3 중량%로 포함된다. 상기 함불소 화합물이 0.01 중량% 미만으로 포함되면 인듐산화막 식각시 잔사가 발생할 수 있으며, 5 중량%를 초과하면 유리 기판 또는 실리콘층의 식각률이 증가하는 문제가 발생한다.
In addition, the fluorine-containing compound is included in an amount of 0.01 to 5% by weight, preferably 0.01 to 3% by weight, based on the total weight of the indium oxide film etchant composition. When the fluorine-containing compound is included in an amount of less than 0.01 wt %, a residue may occur during etching of the indium oxide film, and when it exceeds 5 wt %, an etch rate of the glass substrate or the silicon layer increases.
본 발명의 인듐산화막 식각액 조성물에 포함되는 물은 조성물 총 중량이 100 중량%가 되도록 잔량으로 포함된다. 상기 물은 특별히 한정되지 않으나, 탈이온수를 이용하는 것이 바람직하다. 그리고, 상기 물은 물 속에 이온이 제거된 정도를 보여주는 물의 비저항값이 18㏁·㎝ 이상인 탈이온수를 이용하는 것이 바람직하다.
Water contained in the indium oxide film etchant composition of the present invention is included in the remaining amount so that the total weight of the composition is 100% by weight. The water is not particularly limited, but it is preferable to use deionized water. In addition, it is preferable to use deionized water having a specific resistance value of 18 ㏁·cm or more, which shows the degree of removal of ions in the water.
또한, 본 발명의 인듐산화막 식각액 조성물은 추가로 금속 이온 봉쇄제 및 부식 방지제로 이루어진 군으로부터 선택되는 1종 이상을 포함할 수 있다. 또한, 상기 첨가제는 이에만 한정되는 것이 아니라, 본 발명의 효과를 더욱 양호하게 하기 위하여, 당 업계에 공지되어 있는 여러 다른 첨가제들을 선택하여 첨가할 수도 있다.In addition, the indium oxide film etchant composition of the present invention may further include at least one selected from the group consisting of a metal ion sequestrant and a corrosion inhibitor. In addition, the additive is not limited thereto, and in order to further improve the effect of the present invention, various other additives known in the art may be selected and added.
본 발명의 인듐산화막 식각액 조성물의 성분들은 통상적으로 공지된 방법에 의하여 제조 가능하며, 반도체 공정용의 순도로 사용하는 것이 바람직하다.
The components of the indium oxide film etchant composition of the present invention can be prepared by a conventionally known method, and it is preferable to use the indium oxide film etchant composition with purity for semiconductor processing.
또한, 본 발명은 Also, the present invention
(1)기판 상에 인듐산화막을 형성하는 단계;(1) forming an indium oxide film on a substrate;
(2)상기 인듐산화막 상에 선택적으로 광반응 물질을 남기는 단계; 및(2) selectively leaving a photoreactive material on the indium oxide layer; and
(3)상기 본 발명의 인듐산화막 식각액 조성물을 사용하여 상기 인듐산화막을 식각하는 단계를 포함하는 인듐산화막의 식각방법에 관한 것이다.(3) It relates to an etching method of an indium oxide film comprising the step of etching the indium oxide film using the indium oxide film etchant composition of the present invention.
본 발명의 식각방법에서, 상기 광반응 물질은 통상적인 포토레지스트 물질인 것이 바람직하며, 통상적인 노광 및 현상 공정에 의해 선택적으로 남겨질 수 있다.
In the etching method of the present invention, the photoreactive material is preferably a conventional photoresist material, and may be selectively left by a conventional exposure and development process.
또한, 본 발명은 Also, the present invention
(1)기판 상에 게이트 배선을 형성하는 단계;(1) forming a gate wiring on a substrate;
(2)상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계;(2) forming a gate insulating layer on the substrate including the gate wiring;
(3)상기 게이트 절연층 상에 산화물 반도체층을 형성하는 단계;(3) forming an oxide semiconductor layer on the gate insulating layer;
(4)상기 산화물 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및(4) forming source and drain electrodes on the oxide semiconductor layer; and
(5)상기 드레인 전극에 연결된 화소 전극을 형성하는 단계를 포함하는 액정표시장치용 어레이 기판의 제조방법에 있어서,(5) In the method of manufacturing an array substrate for a liquid crystal display device comprising the step of forming a pixel electrode connected to the drain electrode,
상기 (1)단계는 기판 상에 구리/인듐산화막 또는 구리합금/인듐산화막을 형성하고, 상기 구리/인듐산화막 또는 구리합금/인듐산화막을 식각액 조성물로 식각하여 게이트 배선을 형성하는 단계를 포함하고,The step (1) comprises forming a copper/indium oxide film or a copper alloy/indium oxide film on a substrate, and etching the copper/indium oxide film or copper alloy/indium oxide film with an etchant composition to form a gate wiring,
상기 (5)단계는 인듐산화막을 형성하고, 상기 인듐산화막을 식각액 조성물로 식각하여 화소 전극을 형성하는 단계를 포함하며, The step (5) includes forming an indium oxide layer and etching the indium oxide layer with an etchant composition to form a pixel electrode,
상기 식각액 조성물은 본 발명의 인듐산화막 식각액 조성물인 것을 특징으로 하는 액정 표시 장치용 어레이 기판의 제조방법에 관한 것이다.
The etchant composition relates to a method of manufacturing an array substrate for a liquid crystal display, characterized in that the indium oxide film etchant composition of the present invention.
종래의 황산염 또는 초산염을 포함하는 인듐산화막 식각액 조성물은 상기 (5)단계의 화소 전극을 식각할 때, 횡방향의 식각 속도가 느려 사이드 에칭량이 적었다. 그러나 본 발명의 인듐산화막 식각액 조성물은 상기 황산염 및 초산염을 포함하지 않음으로써, 이와 같은 문제점을 해결할 수 있으며, 인듐산화막의 하부막인 구리계 금속막의 손상을 예방할 수 있다.In the conventional indium oxide film etchant composition containing sulfate or acetate, when the pixel electrode in step (5) was etched, the etch rate in the lateral direction was slow and the amount of side etching was small. However, since the indium oxide layer etchant composition of the present invention does not contain the sulfate and acetate, such a problem can be solved and damage to the copper-based metal layer, which is the lower layer of the indium oxide layer, can be prevented.
상기 (1)단계의 기판 상에 형성되는 인듐산화막은 구리/인듐산화막 또는 구리합금/인듐산화막의 다층막이며, 상기 (5)단계에서 형성하는 인듐산화막은 인듐산화막의 단일막이다.The indium oxide film formed on the substrate in step (1) is a copper/indium oxide film or a copper alloy/indium oxide multilayer film, and the indium oxide film formed in the step (5) is a single indium oxide film.
상기 인듐산화막은 인듐주석산화막(ITO), 인듐아연산화막(IZO) 및 인듐갈륨아연산화막(IGZO)으로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것이다.The indium oxide film includes at least one selected from the group consisting of an indium tin oxide film (ITO), an indium zinc oxide film (IZO), and an indium gallium zinc oxide film (IGZO).
본 발명의 인듐산화막 식각액 조성물로 식각하여 상기 (1)단계에서 게이트 배선을 형성할 수 있으며, 상기 (5)단계에서 화소 전극을 형성할 수 있다.
By etching with the indium oxide film etchant composition of the present invention, a gate line may be formed in step (1), and a pixel electrode may be formed in step (5).
상기 액정표시장치용 어레이 기판은 박막트랜지스터(TFT) 어레이 기판일 수 있다.
The array substrate for the liquid crystal display may be a thin film transistor (TFT) array substrate.
또한, 본 발명은Also, the present invention
상기 본 발명의 인듐산화막 식각액 조성물을 사용하여 식각된 게이트 배선 및 화소 전극으로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 액정 표시 장치용 어레이 기판에 관한 것이다.
It relates to an array substrate for a liquid crystal display comprising at least one selected from the group consisting of gate wirings and pixel electrodes etched using the indium oxide film etchant composition of the present invention.
이하에서, 실시예를 통하여 본 발명을 보다 상세히 설명한다. 그러나, 하기의 실시예는 본 발명을 더욱 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 하기의 실시예에 의하여 한정되는 것은 아니다. 하기의 실시예는 본 발명의 범위 내에서 당업자에 의해 적절히 수정, 변경될 수 있다.
Hereinafter, the present invention will be described in more detail through examples. However, the following examples are provided to illustrate the present invention in more detail, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.
<< 인듐산화막indium oxide film 식각액etchant 조성물 제조> Composition Preparation>
실시예Example 1 내지 3 및 1 to 3 and 비교예comparative example 1 내지 10. 1 to 10.
하기 표 1에 나타낸 조성에 따라 실시예 1 내지 3 및 비교예 1 내지 10의 인듐산화막 식각액 조성물을 제조하였으며, 100 중량%가 되도록 잔량의 물을 포함하였다.The indium oxide film etchant compositions of Examples 1 to 3 and Comparative Examples 1 to 10 were prepared according to the compositions shown in Table 1, and the remaining amount of water was included so as to be 100% by weight.
칼륨sulfuric acid
potassium
암모늄acet
ammonium
칼륨chloride
potassium
암모늄nitric acid
ammonium
BTA : benzotriazoleBTA: benzotriazole
ABF : ammonium bifluoride
ABF : ammonium bifluoride
실험예Experimental example 1. One. 인듐산화막indium oxide film 식각액etchant 조성물의 특성 평가 Evaluation of the properties of the composition
유리 기판(100mmⅩ100mm)상에 구리막을 증착시켜 소스/드레인을 형성한후, 상기 구리막 위에 실리콘을 적층하여 홀을 형성함으로써, 소스/드레인의 금속막인 구리를 노출시키게 한다. 그 후, 인듐산화막을 증착시킨 뒤, 포토리소그래피(photolithography) 공정을 통하여 기판 상에 소정의 패턴을 가진 포토레지스트가 형성되도록 한 후, 실시예 1 내지 3 및 비교예 1 내지 10의 인듐산화막 식각액 조성물을 각각 사용하여 인듐산화막에 대하여 식각공정을 실시하였다.After forming a source/drain by depositing a copper film on a glass substrate (100 mm×100 mm), silicon is laminated on the copper film to form a hole, thereby exposing copper, which is a metal film of the source/drain. Thereafter, after depositing an indium oxide film, a photoresist having a predetermined pattern is formed on the substrate through a photolithography process, and then, the indium oxide film etchant composition of Examples 1 to 3 and Comparative Examples 1 to 10 An etching process was performed on the indium oxide film using each.
분사식 식각 방식의 실험장비(모델명 : ETCHER(TFT), SEMES사)를 이용하였고, 식각공정시 식각액 조성물의 온도는 약 35℃ 내외로 하였으나, 적정온도는 다른 공정조건과 기타 요인에 의해 필요에 따라 변경될 수 있다. 식각시간은 식각 온도에 따라서 다를 수 있으나, LCD 에칭 공정에서 통상 50 내지 100초 정도로 진행하였다. 상기 식각공정에서 식각된 상기 인듐산화막의 프로파일을 단면 SEM(Hitachi사 제품, 모델명 S-4700)을 사용하여 검사하였으며, 사이드 에치, 잔사 발생 유무, 유리 식각율 및 하부 금속(Cu) 손상(attack)을 관찰하여 그 결과를 하기 표 2에 나타내었다.Experimental equipment (model name: ETCHER (TFT), SEMES Co., Ltd.) of the spray-type etching method was used, and the temperature of the etchant composition during the etching process was about 35 ° C. can be changed. The etching time may vary depending on the etching temperature, but in the LCD etching process, it was usually performed for about 50 to 100 seconds. The profile of the indium oxide film etched in the etching process was inspected using a cross-sectional SEM (manufactured by Hitachi, model name S-4700). was observed and the results are shown in Table 2 below.
(㎛)side etch
(μm)
(Å/sec)glass etch rate
(Å/sec)
상기 표 2의 결과에서, 본 발명의 인듐산화막 식각액 조성물인 실시예 1 내지 3은 사이드 에치가 우수하며, 잔사가 발생하지 않으며, 유리 식각율도 우수한 결과를 보였으며, 하부막인 구리막에 손상을 가하지 않는 것을 확인할 수 있었다.In the results of Table 2, Examples 1 to 3, which are the indium oxide film etchant compositions of the present invention, have excellent side etching, no residue, and excellent glass etch rate, and damage to the lower copper film. I was able to confirm that it didn't.
반면, 본 발명의 과산화수소 함량을 벗어난 비교예 1 내지 2의 인듐산화막 식각액 조성물은 사이드 에치가 낮거나, 패턴이 유실된 결과를 보였으며, 과산화수소 함량이 본 발명의 함량 미만인 비교예 1의 인듐산화막 식각액 조성물은 잔사가 발생하였다.On the other hand, the indium oxide film etchant compositions of Comparative Examples 1 and 2 outside the hydrogen peroxide content of the present invention showed a low side etch or pattern loss, and the indium oxide film etchant of Comparative Example 1 having a hydrogen peroxide content less than the content of the present invention The composition developed a residue.
아졸 화합물의 함량이 미만인 비교예 3의 인듐산화막 식각액 조성물은 하부막인 구리막에 손상을 가하였으며, 아졸 화합물의 함량을 초과한 비교예 4의 인듐산화막 식각액 조성물은 사이드 에치가 우수하지 못하였으며, 잔사가 발생한 결과를 보였다.The indium oxide film etchant composition of Comparative Example 3, in which the content of the azole compound was less than, damaged the lower copper film, and the indium oxide film etchant composition of Comparative Example 4 exceeding the content of the azole compound did not have excellent side etch, The results showed that residues were generated.
함불소 화합물의 함량이 초과된 비교예 5의 인듐산화막 식각액 조성물은 유리 식각율의 결과가 좋지 못하였다.The indium oxide film etchant composition of Comparative Example 5 in which the content of the fluorine-containing compound was exceeded had poor glass etch rate results.
또한, 황산염을 포함한 비교예 6 및 초산염을 포함한 비교예 7의 인듐산화막 식각액 조성물은 사이드 에치 및 유리 식각율의 결과가 우수하지 못하였고, 잔사가 발생한 것을 확인할 수 있었다.In addition, the indium oxide film etchant composition of Comparative Example 6 containing sulfate and Comparative Example 7 containing acetate did not have excellent side etch and glass etch rates, and it was confirmed that residues were generated.
함불소 화합물을 포함하지 않은 비교예 8, 과수를 포함하지 않은 비교예 9 및 10의 인듐산화막 식각액 조성물은 사이드 에치 결과가 우수하지 못하였으며, 모두 잔사가 발생한 결과를 보였다.
The indium oxide film etchant compositions of Comparative Example 8 not containing the fluorinated compound and Comparative Examples 9 and 10 containing no fruit tree did not have excellent side etch results, and all of them showed residues.
따라서, 본 발명의 인듐산화막 식각액 조성물은 황산염 및 초산염으로 이루어진 군으로부터 선택되는 1종 이상을 포함하지 않음으로써, 사이드 에치 및 유리 식각율의 효과를 증대시킬 수 있다.Therefore, the indium oxide film etchant composition of the present invention does not contain at least one selected from the group consisting of sulfate and acetate, thereby increasing the effects of side etch and glass etch rate.
또한, 본 발명의 인듐산화막 식각액 조성물은 식각시 잔사가 발생하지 않으며, 액정 표시 장치용 어레이 기판의 제조에서 인듐산화막의 하부막인 구리막에 손상을 가하지 않아 구리막인 소스/드레인 전극의 단선 불량을 방지할 수 있으며, 인듐산화막을 효과적으로 식각할 수 있다.In addition, the indium oxide film etchant composition of the present invention does not generate a residue during etching, and does not damage the copper film, which is the lower film of the indium oxide film, in the manufacture of an array substrate for a liquid crystal display, so that the source/drain electrode, which is a copper film, is disconnected poorly. can be prevented, and the indium oxide film can be effectively etched.
Claims (13)
인듐산화막 식각액 조성물 총 중량에 대하여, 질산 8 내지 30 중량%, 아졸 화합물 0.1 내지 10 중량%, 함불소 화합물 0.01 내지 5 중량% 및 인듐산화막 식각액 조성물 총 중량이 100 중량%가 되도록 잔량의 물을 포함하는 것을 특징으로 하는 인듐산화막 식각액 조성물.Does not contain sulfates, acetates and hydrogen peroxide;
Based on the total weight of the indium oxide film etchant composition, 8 to 30% by weight of nitric acid, 0.1 to 10% by weight of the azole compound, 0.01 to 5% by weight of the fluorine-containing compound, and the remaining amount of water so that the total weight of the indium oxide film etchant composition is 100% by weight Indium oxide film etchant composition, characterized in that.
(2)상기 인듐산화막 상에 선택적으로 광반응 물질을 남기는 단계; 및
(3)청구항 1 내지 청구항 7 중 어느 한 항의 인듐산화막 식각액 조성물을 사용하여 상기 인듐산화막을 식각하는 단계를 포함하는 인듐산화막의 식각방법.(1) forming an indium oxide film on a substrate;
(2) selectively leaving a photoreactive material on the indium oxide layer; and
(3) An etching method of an indium oxide film comprising the step of etching the indium oxide film using the indium oxide film etchant composition of any one of claims 1 to 7.
상기 광반응 물질은 포토레지스트 물질로, 노광 및 현상 공정에 의해 선택적으로 남겨지는 것임을 특징으로 하는 인듐산화막의 식각방법.9. The method of claim 8,
The photoreactive material is a photoresist material, and the method for etching an indium oxide film, characterized in that it is selectively left by an exposure and development process.
(2)상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계;
(3)상기 게이트 절연층 상에 산화물 반도체층을 형성하는 단계;
(4)상기 산화물 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및
(5)상기 드레인 전극에 연결된 화소 전극을 형성하는 단계를 포함하는 액정표시장치용 어레이 기판의 제조방법에 있어서,
상기 (1)단계는 기판 상에 구리/인듐산화막 또는 구리합금/인듐산화막을 형성하고, 상기 구리/인듐산화막 또는 구리합금/인듐산화막을 식각액 조성물로 식각하여 게이트 배선을 형성하는 단계를 포함하고,
상기 (5)단계는 인듐산화막을 형성하고, 상기 인듐산화막을 식각액 조성물로 식각하여 화소 전극을 형성하는 단계를 포함하며,
상기 식각액 조성물은 청구항 1 내지 청구항 7 중 어느 한 항의 인듐산화막 식각액 조성물인 것을 특징으로 하는 액정 표시 장치용 어레이 기판의 제조방법.(1) forming a gate wiring on a substrate;
(2) forming a gate insulating layer on the substrate including the gate wiring;
(3) forming an oxide semiconductor layer on the gate insulating layer;
(4) forming source and drain electrodes on the oxide semiconductor layer; and
(5) In the method of manufacturing an array substrate for a liquid crystal display device comprising the step of forming a pixel electrode connected to the drain electrode,
Step (1) includes forming a copper/indium oxide film or a copper alloy/indium oxide film on a substrate, and etching the copper/indium oxide film or copper alloy/indium oxide film with an etchant composition to form a gate wiring,
The step (5) includes forming an indium oxide layer and etching the indium oxide layer with an etchant composition to form a pixel electrode,
The etchant composition is a method of manufacturing an array substrate for a liquid crystal display, characterized in that the indium oxide film etchant composition according to any one of claims 1 to 7.
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